Fluorine-containing polymerizable monomer and polymer compound using same

ABSTRACT

The present invention relates to a fluorine-containing polymerizable monomer represented by the formula [1], 
     [Chem. 31] 
                         
wherein “a” represents an integer of 1-4. This monomer has a plurality of polymerizable amines in the molecule and at the same time a hexafluoroisopropyl group(s). With this, it can be used as an effective polymerizable monomer, which can exhibit water repellency, oil repellency, low water absorptive property, heat resistance, weather resistance, corrosion resistance, transparency, photosensitivity, low refractive index property, low dielectric property, etc., and can be used for advanced polymer material fields.

TECHNICAL FIELD

The present invention relates to a novel fluorine-containingpolymerizable monomer and a novel polymer compound using the same.

BACKGROUND OF THE INVENTION

Polyamide and polyimide have been developed as representatives oforganic polymers having high-degree heat resistance. They form a largemarket in electronic device field, engineering plastic field such asautomotive and aerospace uses, fuel cell field, medical material field,optical material field, etc. At their center, many various polymers areput into practical use, such as polyimide represented by nylon, KEVLAR,etc.; polyamide acid and polyimide, which can be representativeheat-resistant polymers; polyamide imide, which is a composite of them;and polybenzoxazole, polybenzthiazole, polybenzimidazole, etc. Inparticular, polyimide is again recently attracting attention as amaterial that is resistant to a lead-free solder step.

Polymerization of many of these heat-resistant polymers is conducted bysuccessively generating a reaction, such as polyaddition orpolycondensation, using plural types of monomers having a bifunctionalor trifunctional reactive group in the molecule.

Regarding combinations of monomers in polymerization, there are known,in the case of polyamide, a method in which a diamine-type monomer iscondensed with a dicarboxylic acid derivative, such as dicarboxylicacid, acid chloride or ester, and, in the case of polyamide acid orpolyimide, a method by a polyaddition of diamine and acid dianhydride.As diamines that are generally used, aliphatic diamines, alicyclicdiamines and aromatic diamines have been reported. From the viewpoint ofpolymerizability and heat resistance, however, there is preferably usedan aniline-series monomer that has a supporting skeleton of a benzenesingle ring, biphenyl-type or polycyclic structure, in which a pluralityof benzene rings are directly or indirectly bonded together, and thatcontains a plurality of amines in the molecule. On the other hand, inthe case of polybenzoxazole and polybenzthiazole, there are usedmonomers having amine and hydroxyl group and amine and thiol group atortho-positions of the benzene ring.

The purpose of simultaneously having an amine and another functionalgroup in the molecule is explained, as follows. That is, there isconducted a design in which diamine is used as a polymerization site andat the same time hydroxyl group and thiol group are used as functionalgroups for intramolecular condensation cyclization, and in which aphenolic acid group is contained as a photosensitive functional group ofthese alkali-soluble groups and the like. However, there are reports ofonly the above-mentioned limited combinations in an attempt to containplural types of functional groups together with diamine.

On the other hand, fluoro compounds have been developed or put intopractical use in wide material fields, such as polyolefins andcondensation polymers, mainly in advanced material fields, due tocharacteristics possessed by fluorine, such as water repellency, oilrepellency, low water absorptive property, heat resistance, weatherresistance, corrosion resistance, transparency, photosensitivity, lowrefractive index property and low dielectric property. In thecondensation polymer field, an attempt to introduce fluorine into adiamine monomer has been conducted. There are reports of a diaminemonomer in which hydrogen of the benzene ring has been replaced withfluorine atom or trifluoromethyl group, a diamine monomer in which ahexafluoroisopropenyl group has been introduced between two aromaticrings, and a fluorine-containing diamine monomer in which the benzenering has been subjected to a hydrogen reduction. Furthermore, abishydroxyamine monomer having a hexafluoroisopropenyl group as acentral atomic group and aromatic hydroxyamines at its both sides hasalso been put into practical use. In this case, it is applied as apolybenzoxazole or hydroxyl-containing polyimide. They are explained,for example, as fluorine-containing polybenzazoles in Non-patentPublication 1, etc.

Furthermore, on the other hand, there have recently been conductedactive researches and developments on photoresist materials, in whichtransparency of fluoro compounds in ultraviolet region, particularly invacuum ultraviolet region, has been applied. It is an attempt to achieveadhesion to substrate, high glass transition point, photosensitivity dueto acidity of fluorocarbinol group, alkali development property, etc.,while achieving transparency at each wavelength for use by introducingfluorine. In particular, of fluorocarbinols, hexafluoroisopropyl groupattracts attention due to its dissolution behavior, non-swellingproperty, high contrast, etc., and many researches and developments areconducted.

As assumed from photoresist development examples, hexafluoroisopropylgroup, which is an acidic alcohol, has a potential for achieving arapid, homogeneous, alkali solubility, while it maintains less swellingproperty. There have been, however, few reports of development examplesof heat resistant polymers using a similar concept, that is, heatresistant polymers containing a hexafluoroisopropyl group as an acidicalcohol. Carboxylic group can be cited as a general acidic group.However, due to its high reactivity with amine, they say that it isdifficult to make an amine having a carboxylic group in the samemolecule exist stably.

Non-patent Publication 1: “Latest Polyimide, its basic and application”edited by Japan Polyimide Study Group, page 426.

SUMMARY OF THE INVENTION

It is an object of the present invention to find a novel, polymerizablemonomer for polymer materials, which has surface characteristics (waterrepellency, oil repellency, etc.), resistances (heat resistance, weatherresistance, corrosion resistance, etc.) and other characteristics(transparency, low refractive index property, low dielectric property,etc.) as fluorine-containing materials, together with alkali solubility,photosensitivity, organic solvent dissolution property, etc., and toprovide a novel polymer compound using the same.

The present inventors have repeated an eager examination to solve theabove-mentioned task. As a result, we have found a novel phenylenediamine compound that has a phenylene diamine skeleton and ahexafluoroisopropyl group(s) substituted for at least one hydrogen atomon the phenylene diamine. Furthermore, we have found that, in the caseof a specific monomer having a hexafluoroisopropyl group at an orthoposition of the amine, it involves a cyclization reaction, resulting ina novel polymer compound having many characteristics such as lowdielectric property, heat resistance and solvent resistance, therebycompleting the present invention.

That is, according to the present invention, there is provided afluorine-containing polymerizable monomer represented by the formula [1]

wherein “a” represents an integer of 1-4.

Furthermore, according to the present invention, there is provided apolymer compound derived from the fluorine-containing polymerizablemonomer.

DETAILED DESCRIPTION

As mentioned above, it is possible to provide a novel, phenylene diaminetype, fluorine-containing, polymerizable monomer having afluorocarbinol-type acidic group and a novel polymer compound using thesame, by containing diamine and hexafluoroisopropyl group at the sametime.

A fluorine-containing polymerizable monomer of the present invention hasa plurality of polymerizable amines in the molecule and at the same timea hexafluoroisopropyl group(s). With this, it can be used as aneffective polymerizable monomer, which can exhibit water repellency, oilrepellency, low water absorptive property, heat resistance, weatherresistance, corrosion resistance, transparency, photosensitivity, lowrefractive index property, low dielectric property, etc., and can beused for advanced polymer material fields. Furthermore, sincehexafluoroisopropyl group is an acidic group having alkali solubility,it can also be used as a photosensitive insulating film for electronicdevices, which has low dielectric property, high dissolution, highcontrast, etc. The above fluorine-containing polymerizable monomerrepresented by the formula [1] may be a fluorine-containingpolymerizable monomer represented by the following formula [2] orformula [3] (in the formulas [2] and [3], the definition of “a” is thesame as that of the formula [1]).

Furthermore, the above fluorine-containing polymerizable monomerrepresented by the formula [1] may be1-(2-hydroxyhexafluoro-2-propyl)-2,5-phenylenediamine, which isrepresented by the formula [4].

As the polymerizable monomer of the formula [1] is specificallyexemplified, the following formulas [4], [9a], [9b], [9c] and [10] to[27] are cited.

Herein, a synthesis method of1-(2-hydroxyhexafluoro-2-propyl)-2,5-phenylenediamine, which is amonomer represented by the formula [4],

as a representative example of the formula [1] is explained.

This monomer is obtained by reacting 1,4-phenylenediamine withhexafluoroacetone or hexafluoroacetone trihydrate.

In the case of using hexafluoroacetone, the reaction is conducted byintroducing hexafluoroacetone into 1,4-phenylenediamine as a rawmaterial. Since boiling point of hexafluoroacetone is low (−28° C.), itis preferable to use an apparatus (a cooling apparatus or sealedreactor) for preventing outflow of hexafluoroacetone toward the outsideof the reaction system. A sealed reactor is particularly preferable asthe apparatus.

In the case of using hexafluoroacetone trihydrate, the reaction can bestarted by mixing together 1,4-phenylene diamine as a raw material andhexafluoroacetone trihydrate at the same time. Since boiling point ofhexafluoroacetone trihydrate is relatively high (105° C.), its handlingis easy as compared with hexafluoroacetone (boiling point: −28° C.). Inthis case, a sealed container can also be used. It is, however, possibleto sufficiently prevent outflow of hexafluoroacetone trihydrate towardthe outside of the reaction system, even by allowing tap water (roomtemperature) to flow through a normal reflux condenser.

Hexafluoroacetone has a reactivity higher than that of hexafluoroacetonetrihydrate. Depending on the reaction condition, hexafluoroacetonereacts with an amino group on the aniline skeleton. With this, it islikely to generate by-products (imines) represented by the followingformulas [28] to [30].

As mentioned hereinabove, it is particularly preferable to usehexafluoroacetone trihydrate in the production of1-(2-hydroxyhexafluoro-2-propyl)-2,5-phenylene diamine from theviewpoints of handling easiness, apparatus simplicity and high productselectivity.

The amount of hexafluoroacetone or hexafluoroacetone trihydrate ispreferably one equivalent to 10 equivalents, more preferably 1.5equivalents to 5 equivalents, relative to 1,4-phenylene diamine. Thereaction proceeds without problem even by using more than this, but itis not preferable from economical viewpoint.

The present reaction is conducted normally in a temperature range ofroom temperature to 180° C., preferably 50° C. to 150° C., particularlypreferably 90° C. to 130° C. A temperature exceeding 180° C. is notpreferable, since side reactions proceed.

Although the present reaction can be conducted without using catalyst,it is possible to accelerate the reaction by using an acid catalyst. Asthe catalyst used, aluminum chloride, iron (III) chloride, Lewis acidssuch as boron fluoride, and organic sulfonic acids such asbenzenesulfonic acid, camphorsulfonic acid (CSA), methanesulfonic acid,p-toluenesulfonic acid (pTsOH), paratoluenesulfonic acid (pTsOH)monohydrate and pyridiniumparatoluene sulfonate (PPTS) are preferable.Of these, aluminum chloride, iron (III) chloride, methanesulfonic acidand p-toluenesulfonic acid (pTsOH) monohydrate are particularlypreferable. The amount of the catalyst used is preferably 0.5 mol % to10 mol %, particularly preferably 1 mol % to 5 mol %, relative to onemole of 1,4-phenylene diamine. The reaction proceeds without problemeven by using more than this, but it is not preferable from economicalviewpoint.

Although the present reaction can be conducted without using solvent, itis also possible to use solvent. The solvent to be used is notparticularly limited as long as it is not involved in the reaction. Anaromatic hydrocarbon such as xylene or water is preferable. The amountof the solvent to be used is not particularly limited, but the use in alarge amount is not preferable since yield per volume lowers.

In the case of conducting the present reaction in a sealed reactor(autoclave), the mode is different depending on the use ofhexafluoroacetone or hexafluoroacetone trihydrate. In the case of usinghexafluoroacetone, the reactor is charged firstly with 1,4-phenylenediamine and according to need catalyst and/or solvent. Then, it ispreferable to successively introduce hexafluoroacetone, while increasingthe temperature in a manner that the reactor inside pressure does notexceed 0.5 MPa. In the case of using hexafluoroacetone trihydrate, it ispossible to firstly introduce 1,4-phenylene diamine and a necessaryamount of hexafluoroacetone trihydrate. Furthermore, according to need,it is possible to conduct the reaction by introducing catalyst and/orsolvent into the reactor.

Although the reaction time of the present reaction is not particularlylimited, the optimum reaction time is different depending on thetemperature, the amount of catalyst used, etc. Therefore, it ispreferable to terminate the present step, after confirming that the rawmaterial has sufficiently been consumed by conducting the reaction,while measuring the progress condition of the reaction by ageneral-purpose analysis means such as gas chromatography. After thetermination of the reaction, it is possible to obtain1-(2-hydroxyhexafluoro-2-propyl)-2,5-phenylene diamine by normal meanssuch as extraction, distillation and crystallization. According to need,it is also possible to conduct a purification by column chromatographyor recrystallization, etc.

The production of other fluorine-containing polymerizable monomersrepresented by the formula [1] can be conducted in accordance with theabove-mentioned synthesis method of1-(2-hydroxyhexafluoro-2-propyl)-2,5-phenylene diamine, exceptcontrolling the amount of hexafluoroacetone or hexafluoroacetonetrihydrate used.

Next, an exemplary method for using a fluorine-containing polymerizablemonomer according to the present invention is explained. Thefluorine-containing polymerizable monomer of the present invention is adiamine and is a compound having at least one hexafluoroisopropyl group,and has at least three functional groups at the same time in themolecule. In the case of producing a polymer, these at least threefunctional groups are effectively used. Specifically, it is preferableto use diamine.

It is possible to use a dicarboxylic acid monomer as a partner of thediamine, which is the fluorine-containing polymerizable monomer of thepresent invention, thereby synthesizing a polyamide resin as a polymerproduced. In this case, it is possible to use dicarboxylic acid monomerand its derivatives such as dicarboxylic acid dihalides (halogen ischlorine, bromine, fluorine, or iodine), dicarboxylic acid monoesters,and dicarboxylic acid diesters.

As a polymerizable monomer that becomes a partner of thefluorine-containing polymerizable monomer of the present invention isexemplified, there are cited dicarboxylic acids and their esterderivatives, which are represented by the formula [31] and dicarboxylicacid halides, which are represented by the formula 32].

In the formulas [31] and [32], each R is independently a hydrogen; analkyl group such as methyl, ethyl, propyl, isopropyl or butyl group; abenzyl group, or the like. B is a bivalent organic group containing atleast one selected from aliphatic rings, aromatic rings and alkylenegroups, it may contain fluorine, chlorine, oxygen, sulfur or nitrogen,and its hydrogens may be partially replaced with alkyl group,fluoroalkyl group, carboxylic group, hydroxyl group or cyano group. Xrepresents a halogen atom (chlorine, fluorine, bromine or iodine).

As the dicarboxylic acid usable in the present invention is exemplifiedin the form of dicarboxylic acid, it can be exemplified by aliphaticdicarboxylic acids such as oxalic acid, malonic acid, succinic acid,glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid,and sebacic acid; and aromatic dicarboxylic acids such as phthalic acid,isophthalic acid, terephthalic acid, 3,3′-dicarboxyldiphenyl ether,3,4′-dicarboxyldiphenyl ether, 4,4′-dicarboxyldiphenyl ether,3,3′-dicarboxyldiphenylmethane, 3,4′-dicarboxyldiphenylmethane,4,4′-dicarboxyldiphenylmethane, 3,3′-dicarboxyldiphenyldifluoromethane,3,3′-dicarboxyldiphenyldifluoromethane,3,4′-dicarboxyldiphenyldifluoromethane,4,4′-dicarboxyldiphenyldifluoromethane, 3,3′-dicarboxyldiphenyl sulfone,3,4′-dicarboxyldiphenyl sulfone, 4,4′-dicarboxyldiphenyl sulfone,3,3′-dicarboxyldiphenyl sulfide, 3,4-dicarboxyldiphenyl sulfide,4,4′-dicarboxyldiphenyl sulfide, 3,3′-dicarboxyldiphenyl ketone,3,4′-dicarboxyldiphenyl ketone, 4,4′-dicarboxyldiphenyl ketone,2,2-bis(3-carboxyphenyl)propane, 2,2-bis(3,4′-dicarboxyphenyl)propane,2,2-bis(4-carboxyphenyl)propane,2,2-bis(3-carboxyphenyl)hexafluoropropane,2,2-bis(3,4′-dicarboxyphenyl)hexafluoropropane,2,2-bis(4-carboxyphenyl)hexafluoropropane,1,3-bis(3-carboxyphenoxy)benzene, 1,4-bis(3-carboxyphenoxy)benzene,1,4-bis(4-carboxyphenoxy)benzene,3,3′-(1,4-phenylenebis(1-methylethylidene))bisbenzoic acid,3,4′-(1,4-phenylenebis(1-methylethylidene))bisbenzoic acid,4,4′-(1,4-phenylenebis(1-methylethylidene))bisbenzoic acid,2,2-bis(4-(3-carboxyphenoxy)phenyl)propane,2,2-bis(4-(4-carboxyphenoxy)phenyl)propane,2,2-bis(4-(3-carboxyphenoxy)phenyl)hexafluoropropane,2,2-bis(4-(4-carboxyphenoxy)phenyl)hexafluoropropane,bis(4-(3-carboxyphenoxy)phenyl)sulfide,bis(4-(4-carboxyphenoxy)phenyl)sulfide,bis(4-(3-carboxyphenoxy)phenyl)sulfone,bis(4-(4-carboxyphenoxy)phenyl)sulfone; perfluorononenyloxygroup-containing dicarboxylic acids such as5-(perfluorononenyloxy)isophthalic acid, 4-(perfluorononenyloxy)phthalicacid, 2-(perfluorononenyloxy)terephthalic acid, and4-methoxy-5-(perfluorononenyloxy)isophthalic acid; andperfluorohexenyloxy group-containing dicarboxylic acids such as5-(perfluorohexenyloxy)isophthalic acid, 4-(perfluorohexenyloxy)phthalicacid, 2-(perfluorohexenyloxy)terephthalic acid, and4-methoxy-5-(perfluorohexenyloxy)isophthalic acid.

By conducting a polymerization using a monomer represented by any of theformulas [1] to [4], there is obtained a polymer compound represented bythe formula [5],

wherein “a” represents an integer of 1-4. B is a bivalent organic groupcontaining at least one selected from aliphatic rings, aromatic ringsand alkylene groups, it may contain fluorine, chlorine, oxygen, sulfuror nitrogen, and its hydrogens may be partially replaced with alkylgroup, fluoroalkyl group, carboxylic group, hydroxyl group or cyanogroup. “n” represents polymerization degree.

As one example of the polymerization reaction, for example, if afluorine-containing polymerizable monomer represented by the formula [1]of the present invention is reacted with the above dicarboxylic acidmonomer (formula [31] or formula [32]), a polymer compound (polyamideresin) represented by the formula [5] is obtained.

This polymerization reaction is not particularly limited in terms ofmethod and condition. For example, it is possible to cite a method inwhich the above diamine component and an amide-forming derivative of theabove dicarboxylic acid are mutually dissolved (melted) at 150° C. orhigher to have a reaction without solvent, a method in which thereaction is conducted at high temperature (preferably 150° C. or higher)in an organic solvent, and a method in which the reaction is conductedat a temperature of −20 to 80° C. in an organic solvent.

Usable organic solvent is not particularly limited, as long as bothcomponents of the raw materials are dissolved therein. It can beexemplified by amide solvents such as N,N-dimethylformamide,N,N-dimethylacetamide, N-methylformamide, hexamethylphosphoric acidtriamide, and N-methyl-2-pyrollidone; aromatic solvents such as benzene,anisole, diphenyl ether, nitrobenzene, and benzonitrile; halogen-seriessolvents such as chloroform, dichloromethane, 1,2-dichloroethane, and1,1,2,2-tetrachloroethane; and lactones such as γ-butyrolactone,γ-valerolactone, δ-valerolactone, γ-caprolactone, ∈-caprolactone,α-methyl-γ-butyrolactone. It is effective to conduct the reaction withsuch organic solvent under coexistence with an acid acceptor such aspyridine and triethylamine. In particular, if the above amide solventsare used, these solvents themselves become acid acceptors. Therefore, itis possible to obtain polyamide resins of high degree of polymerization.

A fluorine-containing polymerizable monomer of the present invention canturn into copolymers by combinations with other diamines anddihydroxyamine, etc. The combinable diamine compound can be exemplifiedby 3,5-diaminobenzotrifluoride, 2,5-diaminobenzotrifluoride,3,3′-bistrifluoromethyl-4,4′-diaminobiphenyl,3,3′-bistrifluoromethyl-5,5′-diaminobiphenyl,bis(trifluoromethyl)-4,4′-diaminodiphenyl, bis(fluorinatedalkyl)-4,4′-diaminodiphenyl, dichloro-4,4′-diaminodiphenyl,dibromo-4,4′-diaminodiphenyl, bis(fluorinatedalkoxy)-4,4′-diaminodiphenyl, diphenyl-4,4′-diaminodiphenyl,4,4′-bis(4-aminotetrafluorophenoxy)tetrafluorobenzene,4,4′-bis(4-aminotetrafluorophenoxy)octafluorobiphenyl,4,4′-binaphthylamine, o-, m- and p-phenylenediamines,2,4-diaminotoluene, 2,5-diaminotoluene, 2,4-diaminoxylene,2,4-diaminodurene, dimethyl-4,4′-diaminodiphenyl,dialkyl-4,4′-diaminodiphenyl, dimethoxy-4,4′-diaminodiphenyl,diethoxy-4,4′-diaminodiphenyl, 4,4′-diaminodiphenylmethane,4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether,4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone,4,4′-diaminobenzophenone, 3,3′-diaminobenzophenone,1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene,1,4-bis(4-aminophenoxy)benzene, 4,4′-bis(4-aminophenoxy)biphenyl,bis(4-(3-aminophenoxy)phenyl)sulfone,bis(4-(4-aminophenoxy)phenyl)sulfone,2,2-bis(4-(4-aminophenoxy)phenyl)propane,2,2-bis(4-(4-aminophenoxy)phenyl)hexafluoropropane,2,2-bis(4-(3-aminophenoxy)phenyl)propane,2,2-bis(4-(3-aminophenoxy)phenyl)hexafluoropropane,2,2-bis(4-(4-amino-2-trifluoromethylphenoxy)phenyl)hexafluoropropane,2,2-bis(4-(3-amino-5-trifluoromethylphenoxy)phenyl)hexafluoropropane,2,2-bis(4-aminophenyl)hexafluoropropane,2,2-bis(3-aminophenyl)hexafluoropropane,2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane,2,2-bis(3-amino-4-methylphenyl)hexafluoropropane,4,4′-bis(4-aminophenoxy)octafluorobiphenyl, 4,4′-diaminobenzanilide,etc. At least two of these can be combined.

Regarding a fluorine-containing polymerizable monomer of the presentinvention, it is also possible to protect the hexafluoropropyl group andintroduce a protecting group (acid-labile group) that is released byacid. Acid-labile groups can be used without limitation, as long as theyare groups that generate release by the effect of photoacid generator,hydrolysis, etc. As specific examples, it is possible to citealkoxycarbonyl groups such as tert-butoxycarbonyl group,tert-amyloxycarbonyl group, methoxycarbonyl group, and ethoxycarbonylgroup; acetal groups such as methoxymethyl group, ethoxyethyl group,butoxyethyl group, cyclohexyloxyethyl group, and benzyloxyethyl group;silyl groups such as trimethylsilyl group, ethyldimethylsilyl group,methyldiethylsilyl group, and triethylsilyl group; acyl groups such asacetyl group, propionyl group, butyryl group, heptanoyl group, hexanoylgroup, valeryl group, and pivaloyl group.

By introducing an acid-releasing group, a polymer compound obtained bypolymerization using a fluorine-containing polymerizing monomer of thepresent invention can be used as a resist material. That is, thehexafluoroisopropanol group in the molecule is protected with anacid-labile protecting group. Then, it is mixed with a photoacidgenerator to produce a resist. By exposing this, the acid labile groupis released, thereby forming a hexafluoroisopropanol group. As a result,an alkali development becomes possible. Thus, it is useful as apositive-type resist or photosensitive material.

A fluorine-containing polymerizing monomer of the present invention canbe used with other functional groups. For example, it is possible tointroduce a crosslinking site by providing an unsaturated bond. Forexample, if a fluorine-containing polymerizing monomer of the presentinvention is reacted with maleic anhydride, it turns into abismaleimide. With this, it is possible to introduce a double bond. Thiscompound is useful as a crosslinking agent.

By dehydrating a polymer compound represented by the formula [5] of thepresent invention, it can be cyclized. As one example, a polymercompound represented by the formula [6] is obtained by subjecting acompound (for example, the following formula [5-1]), which is a polymercompound represented by the formula [5], in which a=1, and which has2-hydroxyhexafluoro-2-propyl group at α-position of the amino group, tocyclization (cyclization condensation). In the following formulas, B isa bivalent organic group containing at least one selected from aliphaticrings, aromatic rings and alkylene groups, it may contain fluorine,chlorine, oxygen, sulfur or nitrogen, and its hydrogens may be partiallyreplaced with alkyl group, fluoroalkyl group, carboxylic group, hydroxylgroup or cyano group. “n” represents degree of polymerization.

The cyclization reaction is not particularly limited. The cyclizationcan be conducted by various methods that accelerate the dehydrationcondition, such as heat and acid catalyst. The cyclization is possible,for example, by heating up to a temperature of 200° C. to 500° C. or bytreatment with a hydrochloric acid aqueous solution of 1M to 12M.

In the case of cyclization, it is possible to conduct a resinmodification accompanied with significant changes in terms of physicalproperties, such as heat resistance improvement, dissolution change,lowering in refractive index and dielectric constant, and achievement ofwater repellency and oil repellency. In particular, afluorine-containing polymer compound represented by the formula [6] ofthe present invention is further improved in heat resistance, since ithas a cyclic structure in the molecule.

As a partner of the diamine, which is a fluorine-containingpolymerizable monomer of the present invention, it is possible to use atetracarboxylic acid derivative, for example, a tetracarboxylic aciddianhydride represented by the formula [33]

wherein R¹ is a tetravalent organic group containing at least oneselected from aliphatic rings, aromatic rings and alkylene groups, itmay contain fluorine, chlorine, oxygen, sulfur or nitrogen, and itshydrogens may be partially replaced with alkyl group, fluoroalkyl group,carboxylic group, hydroxyl group or cyano group. The tetracarboxylicacid dianhydride of this case can be used without particular limitation,as long as it has a structure generally used as a polyamide acid orpolyimide raw material.

Such tetracarboxylic acid dianhydride is not particularly limited instructure. For example, it is possible to cite benzenetetracarboxylicacid dianhydride (pyromellitic acid dianhydride; PMDA),trifluoromethylbenzenetetracarboxylic acid dianhydride,bistrifluoromethylbenzenetetracarboxylic acid dianhydride,difluorobenzenetetracarboxylic acid dianhydride,naphthalenetetracarboxylic acid dianhydride, biphenyltetracarboxylicacid dianhydride, terphenyltetracarboxylic acid dianhydride,hexafluoroisopropylidenediphthalic acid dianhydride, oxydiphthalic aciddianhydride, bicyclo(2,2,2)oct-7-ene-2,3,5,6-tetracarboxylic aciddianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropanoic aciddianhydride (6FDA), 2,3,4,5-thiophenetetracarboxylic acid dianhydride,2,5,6,2≡,5≡,6≡-hexafluoro-3,3′,4,4′-biphenyltetracarboxylic aciddianhydride, bis(3,4-dicarboxyphenyl)sulfonic acid dianhydride,3,4,9,10-perylenetetracarboxylic acid dianhydride, etc. In particular,pyromellitic acid and 6FDA are preferable.

These tetracarboxylic acid dianhydrides may be used alone or in amixture of at least two. In the present invention, in connection withthe ratio in use of the tetracarboxylic acid dianhydride and the aminecomponent, it is used in 0.9-1.1 moles, preferably 0.95-1.05 moles, morepreferably 0.98-1.03 moles, relative to 1 mole of the tetracarboxylicacid dianhydride. If it is outside of this range, the molar ratiobalance is lost, and its properties are impaired. Therefore, it is notpreferable.

According to the present invention, there is provided a polymer compoundthat can be synthesized by using a monomer represented by any of theformulas [1] to [4] and that is represented by the formula [7],

wherein “a” is the same as that of the formula [2], R¹ is a tetravalentorganic group containing at least one selected from aliphatic rings,aromatic rings and alkylene groups, it may contain fluorine, chlorine,oxygen, sulfur or nitrogen, and its hydrogens may be partially replacedwith alkyl group, fluoroalkyl group, carboxylic group, hydroxyl group orcyano group. “n” represents degree of polymerization.

As one example of the polymerization reaction, a polymer compound(polyamide acid) represented by the formula [7] is obtained, forexample, by reacting a fluorine-containing polymerizable monomerrepresented by the formula [1] of the present invention with the abovetetracarboxylic acid anhydride. Regarding method and condition of thepolymerization reaction, it is possible to use a polymerization methodand a polymerization condition, which are similar to those of thereactions with dicarboxylic acids. The usable solvent is notparticularly limited, as long as both components of the raw materialsare dissolved therein. It is possible to use a solvent that is similarto those in the reactions with the dicarboxylic acids. It can beexemplified by amide solvents such as N,N-dimethylformamide,N,N-dimethylacetamide, N-methylformamide, hexamethylphosphoric triamide,and N-methyl-2-pyrolidone; aromatic solvents such as benzene, anisole,diphenyl ether, nitrobenzene, and benzonitrile; halogen-series solventssuch as chloroform, dichloromethane, 1,2-dichloroethane, and1,1,2,2-tetrachloroethane; lactones such as γ-butyrolactone,γ-valerolactone, δ-valerolactone, γ-caprolactone, ∈-caprolactone, andα-methyl-γ-butyrolactone. It is effective to conduct the reaction withsuch organic solvent under coexistence with an acid acceptor such aspyridine and triethylamine.

According to the present invention, a polymer compound represented bythe formula [8],

(in the formula [8], a, R¹ and n are the same as those of the formula[7]) is obtained by subjecting the polymer compound represented by theformula [7] to a cyclization condensation.

Furthermore, n (degree of polymerization) in the general formulas [5] to[8] refers to the number (a positive integer) of the repeating unitsdepending on the degree of polymerization and is preferably 5-10000,more preferably 10-1000. The polymer of the present invention is amixture of polymers having a certain width of polymerization degree. Thepolymer weight average molecular weight is generally preferably 1000 to5000000, particularly preferably 2000 to 200000. The polymerizationdegree and the molecular weight can be set to desired values by suitablyadjusting the after-mentioned polymerization method conditions.

Similar to the reactions with dicarboxylic acids, it can also be turnedinto a copolymer by a combination with other diamines anddihydroxyamines. As a combinable diamine compound, it is possible to usethe above diamine. Similar to the above, it can also be a combination ofat least two.

The above polyamide acid represented by the formula [7] can be turnedinto a fluorine-containing alicyclic polyimide represented by theformula [8] through an imidization reaction by heating or dehydrationagent. In the case of conducting the heating imidization, the treatmentis possible at a temperature of 80-400° C. In particular, a temperaturerange of 150-350° C. is preferable. In case that the imidizationtemperature is lower than 150° C., the degree of imidization is low, andthereby the film strength of the polyimide film is impaired. Therefore,it is not preferable. In case that it exceeds 350° C., the coating filmbecomes colored or brittle. Therefore, it is problematic. It can bechemically conducted by the reaction with a dehydration agent, such asacetic anhydride, in place of the heating treatment.

The fluorine-containing polymer of the present invention can be used inthe condition of a varnish dissolved in an organic solvent or in thepowder condition, film condition, or solid condition. In the case ofusing it as a varnish, it can be applied to a substrate, such as glass,silicon wafer, metal, metal oxide, ceramic, and resin, by a methodnormally used, such as spin coating, spraying, flow coating,impregnation coating, and brush coating.

In the following, the present invention is described in more detail byexamples. The present invention is, however, not limited to theexamples.

Example 1 Production of1-(2-hydroxyhexafluoro-2-propyl)-2,5-phenylenediamine

A 100 ml, glass, sealed container (autoclave) was charged with 10.0 g(92.5 mmol) of 1,4-phenylenediamine, 352 mg (1.85 mmol, 2 mol %) ofp-toluenesulfonic acid monohydrate, and 20 ml of xylene, and the insideof the system was turned into a nitrogen atmosphere. Then, thetemperature increased was started. After the inside temperature of thereaction liquid was set to 100° C., 32.2 g (194 mmol, 2.1 equivalents)of hexafluoroacetone were introduced by spending 50 minutes. After thereaction was conducted at an inside temperature of 120° C. for 1.5hours, the reaction liquid was cooled down. The reaction liquid wasfound by gas chromatography (GC) analysis to contain 47.6% of the targetcompound, 1-(2-hydroxyhexafluoro-2-propyl)-2,5-phenylenediamine, and20.7% of the total of various imines produced by the reaction ofhexafluoroacetone with the amine moiety of 1,4-phenylenediamine.

Example 2 Production of1-(2-hydroxyhexafluoro-2-propyl)-2,5-phenylenediamine (the formula [4])

A 100 ml, glass, sealed container (autoclave) was charged with 10.0 g(92.5 mmol) of 1,4-phenylenediamine, 704 mg (3.70 mmol, 4 mol %) ofp-toluenesulfonic acid monohydrate, and 40.7 g (185 mmol, 2 equivalents)of hexafluoroacetone trihydrate, and the inside of the system was turnedinto a nitrogen atmosphere. Then, the temperature increased was started,and the inside temperature of the reaction liquid was set to 110° C.After stirring for 21 hours, the reaction liquid was cooled down. Thereaction liquid was found by gas chromatography (GC) analysis to contain75.5% of the target compound,1-(2-hydroxyhexafluoro-2-propyl)-2,5-phenylenediamine, 3.6% of1,4-phenylenediamine, and 20.9% of imines produced by the reaction ofhexafluoroacetone with the amine moiety of 1,4-phenylenediamine. 200 mlof water were added to the reaction liquid, and it was cooled down iniced bath. The precipitated solid was filtered and vacuum dried, therebyobtaining 24.7 g (yield: 97%; purity: 78.9%) of crude1-(2-hydroxyhexafluoro-2-propyl)-2,5-phenylenediamine. This crudeproduct was recrystallized in toluene, thereby obtaining 18.6 g (yield:73%; purity; 99.4%) of the target1-(2-hydroxyhexafluoro-2-propyl)-2,5-phenylenediamine.

Properties of 1-(2-hydroxyhexafluoro-2-propyl)-2,5-phenylenediamine

Purple-color powder. Melting point: 184.5-185.5° C. ¹H-NMR (standardsubstance: TMS; solvent: (CD₃)₂CO) σ (ppm): 2.83 (br, 2H), 4.80 (br,2H), 6.71 (dd, 1H, J=2.6, 8.5 Hz), 6.88 (m, 1H), 6.98 (d, 1H, J=8.5 Hz).¹⁹F-NMR (standard substance: CCl₃F; solvent: (CD₃)₂CO) σ (ppm): −75.0(s, 6F).

Example 3

By using 1-(2-hydroxyhexafluoro-2-propyl)-2,5-phenylenediaminesynthesized in Example 2, there was conducted a polymerization reactionwith the following compound (a) of dicarboxylic acid chloride.

In the polymerization, a 100 ml, sufficiently dried, sealed,three-necked, glass flask equipped with a stirrer was charged with 40 gof dimethylacetamide, 10 g of pyridine, and 0.01 moles (2.74 g) of1-(2-hydroxyhexafluoro-2-propyl)-2,5-phenylenediamine, followed bystirring while blowing nitrogen to obtain homogenization, charging with0.01 moles (2.02 g) of the compound (a), terephthalic acid chloride, andconducting the polymerization with stirring for 5 hours. Then, it wasreprecipitated in a large amount of methanol for isolation. The isolatedpolymer (A) was dissolved in γ-butyrolactone, thereby obtaining aγ-butyrolactone solution of the polymer (A) (Weight average molecularweight (Mw) of the polymer (A): 9600).

Example 4

By using the compound (b) and the compound (c) as dicarboxylic aciddichlorides in place of the compound (a) of Example 3, respectivepolymerizations were conducted with1-(2-hydroxyhexafluoro-2-propyl)-2,5-phenylenediamine under similarconditions.

After isolation by conducting a post-treatment similar to that ofExample 3, they were dissolved in γ-butyrolactone, thereby obtainingrespective γ-butyrolactone solutions of polymers (B) and (C) (Weightaverage molecular weight of polymer (B): 10200; and Weight averagemolecular weight of polymer (C): 10000).

Example 5

γ-butyrolactone solutions of polymers (A), (B) and (C) synthesized inExample 3 and Example 4 were applied to glass substrates, followed bydrying at 120° C. for 2 hours, thereby obtaining transparent, toughfilms in respective cases.

Then, the obtained film (thickness: 40 μm) of polymer (A) was subjectedto a heating treatment at 280° C. for 2 hours, thereby obtaining a toughfilm through ring closure into polymer (D) (n represents degree ofpolymerization in the following formula). In the measurement of thermaldecomposition temperature of the obtained film, it was stably maintainedeven at 400° C. Dielectric constant at 1 kHz was 2.8 (Weight averagemolecular weight (Mw) of polymer (D): 10000).

Example 6

By using 1-(2-hydroxyhexafluoro-2-propyl)-2,5-phenylenediamine (theformula [4]) synthesized in Example 2, there were conductedpolymerizations with the following tetracarboxylic acid anhydridecompounds (d), (e) and (f),

In the polymerization, a 100 ml, sufficiently dried, sealed,three-necked, glass flask equipped with a stirrer was charged with 30 gof methyl isobutyl ketone and 0.01 moles (2.74 g) of1-(2-hydroxyhexafluoro-2-propyl)-2,5-phenylenediamine, followed bystirring while blowing nitrogen to obtain homogenization, charging with0.01 moles of the three anhydrides, the compounds (d), (e) and (f), andconducting the polymerization with stirring for 5 hours. Then, they werereprecipitated in a large amount of methanol for isolation. The isolatedpolymers (E), (F) and (G) were each dissolved in γ-butyrolactone,thereby obtaining three of polymer solutions (Weight average molecularweight (Mw) of the polymer (E): 10500; Weight average molecular weight(Mw) of the polymer (F): 9900; and Weight average molecular weight (Mw)of the polymer (G): 10000).

These polymer solutions were applied to silicon wafers, therebyproducing highly-homogeneous, tough, transparent films.

Example 7

γ-butyrolactone solutions were prepared in a manner that the polymers(E), (F) and (G) obtained in Example 6 become 10% in solid content,followed by addition of acetic anhydride and pyridine and stirring at50° C. for 2 hr for mixing, thereby conducting imidizations by chemicalreactions. The obtained polymer solutions were reprecipitated inmethanol, followed by three-times repetitive washing with stirring withclean methanol and then drying at room temperature. Although imidecyclizations were confirmed in the obtained polymer solids, they werefound to be soluble in dimethylacetamide and to be soluble polyimides(H), (I) and (J). Then, dimethylacetamide solutions were respectivelyprepared in a manner that (H), (I) and (J) become 12% in solid content,followed by spin coatings on silicon wafers, thereby obtaining toughfluorine-containing polymer films. On the other hand, the films of thepolymer (E), (F) and (G) were subjected to a heat treatment at 350° C.for 1 hour. With this, similar dehydration reactions occurred, therebyproducing the polyimides (H), (I) and (J).

Then, the thermal decomposition temperatures of the polymers (H), (I)and (J) were measured by DSC (differential scanning calorimeter). Withthis, they showed high heat resistances of 465° C., 450° C. and 420° C.in terms of 5% weight reduction temperature. Furthermore, theirdielectric constants at 1 MHz were measured by using an LCR meter. Withthis, they respectively showed low values of 2.8, 2.6 and 2.4.

1. A fluorine-containing polymerizable monomer represented by theformula [2],

wherein “a” represents an integer of 1-4. 2.1-(2-hydroxyhexafluoro-2-propyl)-2,5-phenylenediamine represented by theformula [4],